Processes for converting biomass-derived feedstocks to chemicals and liquid fuels

ABSTRACT

The present invention provides processes, methods, and systems for converting biomass-derived feedstocks to liquid fuels and chemicals. The method generally includes the reaction of a hydrolysate from a biomass deconstruction process with hydrogen and a catalyst to produce a reaction product comprising one of more oxygenated compounds. The process also includes reacting the reaction product with a condensation catalyst to produce C 4+  compounds useful as fuels and chemicals.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.14/215,283, filed on Mar. 17, 2014, issued as U.S. Pat. No. 9,382,185,which claims the benefit of U.S. provisional Application No. 61/786,788filed on Mar. 15, 2013, which is incorporated by reference herein in itsentirety.

FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under an award providedby the U.S. Department of Energy, Award Nos. DE-EE0003044. Thegovernment has certain rights in the invention.

BACKGROUND OF THE INVENTION

Increasing cost of fossil fuel and environmental concerns havestimulated worldwide interest in developing alternatives topetroleum-based fuels, chemicals, and other products. Biomass (materialderived from living or recently living biological materials) is apossible renewable alternative to petroleum-based fuels and chemicals.

Plant biomass is the most abundant source of carbohydrate in the worlddue to the lignocellulosic materials in its cell walls, making it adesirable source of biomass. Lignocellulosic biomass includes threemajor components: (1) cellulose, a primary sugar source forbioconversion processes, includes high molecular weight polymers formedof tightly linked glucose monomers; (2) hemicellulose, a secondary sugarsource, includes shorter polymers formed of various sugars (e.g.,xylose, mannose, glucose, galactose, etc.); and (3) lignin that includesphenylpropanoic acid moieties polymerized in a complex three dimensionalstructure.

Plant cell walls include up to three layers, the two most common beingprimary cell walls and secondary cell walls. The primary cell wallprovides structure for expanding cells and is composed of majorpolysaccharides (cellulose, hemicellulose, and pectin) and structuralproteins (i.e., glycolproteins). The cellulose microfibrils are linkedvia hemicellulosic tethers to form the cellulose-hemicellulose networkthat is embedded in the pectin matrix. The outer part of the primarycell wall is usually impregnated with cutin (e.g., omega hydroxyl acidsand their derivatives) and wax, forming a permeability barrier known asthe plant cuticle.

The secondary cell wall, which is produced after the cell has finishedgrowing, contains a wide range of additional compounds includingpolysaccharides and lignin. The lignin interpenetrates the cellulose,hemicellulose and pectin of the primary cell wall to provide additionalstrength via covalent cross-linking with the hemicellulose. While therelative composition of polysaccharides varies between plants, celltype, and age, the composition of lignocellulosic biomass is roughly40-50% cellulose, 20-25% hemicellulose, and 25-35% lignin, by weightpercent.

The additional compounds, or minor components, present in both theprimary and secondary walls include a variety of species (e.g.,inorganic materials, color bodies, and waxes) at varying concentrations.Additional minor components may derive from material associated with theproduction, processing, or handling of lignocellulosic biomass, such assoil or fertilizer. The minor components can be divided into twocategories: (1) extractives, non-structural biomass components includingterpenoids, stilbenes, flavonoids, phenolics, aliphatics, lignans,alkanes, and proteinaceous materials; and (2) ash, inorganic componentssuch as aluminum, barium, calcium, iron, potassium, magnesium,manganese, phosphorous, sulfur, chloride, ammonium, sulfate, sulfite,thiol, silica, copper, carbonate, phosphorous, etc.

Very few cost-effective processes exist for efficiently deconstructingbiomass and converting cellulose, hemicellulose, and lignin tocomponents better suited for producing fuels, chemicals, and otherproducts. This is generally because each of cellulose, hemicellulose,and lignin demands distinct processing conditions, such as temperatures,pressures, solvents, catalysts, reaction times, etc., in order toeffectively break apart their polymeric structures. As a result, mostprocesses are effective for converting only specific fractions, such ascellulose and hemicellulose, leaving the remaining fraction(s) behindfor additional processing, or alternative uses.

The deconstruction process can introduce new compounds into thefeedstock from the degradation of the biomass components. For example,deconstruction of biomass results in the deconstruction ofpolysaccharides into more desirable smaller saccharides, for examplemono-, di-, or trisaccharides. The deconstruction process alsointroduces degradation products into the feedstock. The presence ofsugar degradation products like organic acids and cyclic etherssignifies a lowering of the overall yield of desirable saccharides. As aresult, one would expect the presence of sugar degradation products tobe undesirable, and their production should be minimized. Surprisingly,the present methods are not only tolerant of sugar degradation products,but the sugar degradation products improve the effectiveness of theprocess to produce desirable monooxygenates from the biomass-derivedfeedstock

Regardless of the deconstruction process used, the resulting feedstockis likely to contain the desired oxygenated hydrocarbons (e.g. sugars)as well as sugar degradation products, extractives, ash, mineral salts,mineral acids, and other solvents used in the deconstruction. The lattercomponents in the heterogeneous mixture can have an impact on biomassconversion efficiencies. Ash components, even at relatively lowconcentrations, can severely limit thermochemical, biochemical, andcatalytic conversion of biomass by affecting operating temperatures,inhibiting fermentation, and poisoning catalysts. As a result, methodsfor purifying biomass-derived feedstocks prior to conversion andprocesses that are semi-tolerant to extractives and ash components areof interest. The latter could be especially important in making biomassa realistic alternative to petroleum feedstocks, as highly or completelypure feedstocks could carry additional costs, such as capitalexpenditures on equipment and processing systems.

SUMMARY

The invention provides methods for producing oxygenated compounds from abiomass-derived feedstock. The method generally involves providing anaqueous feedstock, catalytically reacting a portion of the aqueousfeedstock with hydrogen in the presence of a catalyst at a reactiontemperature and a reaction pressure to produce a reaction product.

The invention is a method for producing oxygenated compounds from abiomass-derived feedstock, the method comprising: providing an aqueousfeedstock, the aqueous feedstock comprising water; greater than about 20wt % of a plurality of first oxygenated hydrocarbons, the firstoxygenated hydrocarbons selected from the group consisting ofmonosaccharides, disaccharides, trisaccharides, oligosaccharides, andcombinations thereof; between about 1 wt % and about 40 wt % of aplurality of second oxygenated hydrocarbons, the second oxygenatedhydrocarbons comprising sugar degradation products; and ash, wherein theash comprises less than about 75 ppm sulfur and less than about 30 ppmphosphorous; and reacting a portion of the aqueous feedstock withhydrogen in the presence of a catalyst, the catalyst comprising at leastone Group VIII metal, to produce a reaction product comprising one ormore oxygenated compounds selected from the group consisting of analcohol, a ketone, a cyclic ether, a carboxylic acid, an aldehyde, adiol, and a polyol.

In one embodiment, the aqueous feedstock is prepared by a biomassdeconstruction method and the deconstruction method is selected from thegroup consisting of thermochemical biomass deconstruction, enzymaticbiomass deconstruction, catalytic biomass deconstruction, andcombinations thereof. In another embodiment, the aqueous feedstock isfurther prepared by a treatment method and the treatment method isselected from the group consisting of physical separation, chemicalseparation, neutralization, catalytic reaction, and combinationsthereof.

In one embodiment, the aqueous feedstock may comprise greater than 30 wt%, greater than 40 wt %, or greater than 50 wt % of the first oxygenatedhydrocarbons. The aqueous feedstock may also comprise greater than 2 wt%, greater than 3 wt %, greater than 4 wt %, or greater than wt % of thesecond oxygenated hydrocarbons. The aqueous feedstock may also compriseless than 35 wt %, less than 30 wt %, less than 25 wt %, or less than 20wt % of the second oxygenated hydrocarbons. The aqueous feedstock mayalso comprise between 1 wt % and 25 wt % furfurals. The aqueousfeedstock may also comprise the second oxygenated hydrocarbons havinggreater than 2 wt %, greater than 3 wt %, greater than 4 wt %, orgreater than 5 wt % furfurals. The aqueous feedstock may also comprisethe second oxygenated hydrocarbons having less than 20 wt %, less than15 wt %, or less than 10 wt % furfurals.

In one embodiment, the aqueous feedstock may comprise less than 70 ppm,less than 60 ppm, or less than 50 ppm sulfur. The aqueous feedstock mayalso comprise less than 25 ppm phosphorus, less than 20 ppm, less than15 ppm, or less than 10 ppm phosphorus.

In one embodiment, the aqueous feedstock further comprises extractives,lignin, lignin derivatives, solids, or combinations thereof.

In one embodiment, the catalyst further comprises a metal selected fromGroup IVB, Group VB, Group VIB, Group VIIB, Group IB, or theLanthanides.

In one embodiment, the invention further comprises reacting a portion ofthe reaction product with a condensation catalyst at a condensationtemperature and a condensation pressure to produce C₄₊ compoundsselected from the group consisting of a C₄₊ alcohol, a C₄₊ ketone, a C₄₊alkane, a C₄₊ alkene, a C₅₊ cycloalkane, a C₅₊ cycloalkene, an aryl, anda fused aryl. The C₄₊ compounds may be distilled to provide acomposition selected from the group consisting of an aromatic fraction,a gasoline fraction, a kerosene fraction, and a diesel fraction. The C₄₊compounds may also comprise one or more aryls selected from the groupconsisting of benzene, toluene, xylene, para-xylene, meta-xylene, andortho-xylene.

Another aspect of the invention provides for producing oxygenatedcompounds from a biomass-derived feedstock, the method comprising:deconstructing biomass with a deconstruction method to produce anintermediate feedstock, the intermediate feedstock comprising oxygenatedhydrocarbons, ash, extractives, lignin, lignin derivatives, and solids;treating the intermediate feedstock with a treatment method to producean aqueous feedstock, the aqueous feedstock comprising: water; greaterthan 20 wt % of a plurality of first oxygenated hydrocarbons, the firstoxygenated hydrocarbons selected from the group consisting ofmonosaccharides, disaccharides, trisaccharides, oligosaccharides, andcombinations thereof; between 1 wt % and 40 wt % of a plurality ofsecond oxygenated hydrocarbons, the second oxygenated hydrocarbonscomprising sugar degradation products; and ash, wherein the ashcomprises less than 75 ppm sulfur and less than 30 ppm phosphorous; andreacting a portion of the aqueous feedstock with hydrogen in thepresence of a catalyst, the catalyst comprising at least one Group VIIImetal, to produce one or more oxygenated compounds selected from thegroup consisting of an alcohol, a ketone, a cyclic ether, a carboxylicacid, an aldehyde, a diol, and a polyol.

In one embodiment, the deconstruction method is selected from the groupconsisting of thermochemical biomass deconstruction, enzymatic biomassdeconstruction, catalytic biomass deconstruction, and combinationsthereof. In another embodiment, the treatment method is selected fromthe group consisting of physical separation, chemical separation,neutralization, catalytic reaction, and combinations thereof. In oneembodiment, the invention further comprises reacting a portion of theoxygenated compounds with a condensation catalyst at a condensationtemperature and a condensation pressure to produce C₄₊ compoundsselected from the group consisting of a C₄₊ alcohol, a C₄₊ ketone, a C₄₊alkane, a C₄₊ alkene, a C₅₊ cycloalkane, a C₅₊ cycloalkene, an aryl, anda fused aryl.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are process flow diagrams of a first and secondembodiment of a process for converting biomass-derived feedstocks tooxygenated compounds. FIG. 1A is an exemplary flow diagram forconverting oxygenated hydrocarbons to oxygenated compounds. FIG. 1B isan exemplary flow diagram for converting oxygenated hydrocarbons tooxygenated compounds including an optional recycle stream.

FIG. 2 is an exemplary product distribution illustrating the effect offeedstock concentration on the product profile for three differentdeoxygenation catalysts.

FIG. 3 is a flow diagram of an embodiment of a process for producingliquid fuels and chemicals from biomass-derived feedstocks that includesa deoxygenation reactor, a condensation reactor, and a recycle stream.

FIG. 4 is a chart illustrating the product distribution, includingspecies and carbon number, for a gasoline range product producedaccording to one embodiment.

FIG. 5 is a comparison of a conventional jet fuel to a jet fuel producedaccording to one embodiment.

FIG. 6 is an exemplary product distribution illustrating the effect ofup to 5 wt % organic components in the feedstock on the product profilefor three different feedstocks.

FIG. 7 is an exemplary product distribution illustrating the effect ofup to 10 wt % organic components in the feedstock on the product profilefor four different feedstocks.

FIG. 8 is an exemplary product distribution illustrating the effect ofup to 90 ppm sulfur in the feedstock on the product profile for threedifferent feedstocks.

FIG. 9 is an exemplary product distribution illustrating the effect ofup to 27 ppm nitrogen in the feedstock on the product profile for twodifferent feedstocks

DESCRIPTION OF THE INVENTION

Processes, methods, and systems for converting biomass-derivedfeedstocks to liquid fuels and chemicals are described herein. Themethod generally consists of reacting hydrogen and an aqueous feedstockcomprising water, oxygenated hydrocarbons, and ash with a catalyst toproduce a reaction product comprising one of more oxygenated compounds.The method may optionally comprise reacting the reaction product with acondensation catalyst to produce C₄₊ compounds.

The biomass-derived feedstocks of the present invention comprise aplurality of first oxygenated hydrocarbons and a plurality of secondoxygenated hydrocarbons. The first oxygenated hydrocarbons may includemonosaccharides, disaccharides, trisaccharides, oligosaccharides, andcombinations thereof, at amounts greater than 20 wt % of the feedstock.The first oxygenated hydrocarbon may also originate from smaller sugarssuch as monosaccharides or disaccharides like glucose or sucrose or maybe a derivative of a larger polysaccharide like starch, cellulose, orhemicellulose.

The second oxygenated hydrocarbons are generally sugar degradationproducts, and are present at amounts between 1 wt % and 40 wt % of thefeedstock. The process of deconstructing biomass may naturally degradesome of the sugars that would otherwise be available as a firstoxygenated hydrocarbon. Despite the depletion of available firstoxygenated hydrocarbons, the sugar degradation products surprisinglyenhance the overall conversion process of converting oxygenatedhydrocarbon to oxygenated compounds.

A third component of the biomass-derived feedstock is ash. Although ashhas been known to negatively impact catalyst performance, the methods,systems, catalysts, and reactors of the present invention can toleratethe presence of ash. In certain cases, the feedstock may have a high wt% of ash without a significant decrease in overall catalyst performance.

An overview of the reaction system is provided. FIGS. 1A and 1B discloseexemplary methods for producing oxygenated compounds, such as C₄₊O₁₊alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes,diols, triols, and mixtures thereof. The disclosed methods includecatalytically reacting C₄₊O₂₊ oxygenated hydrocarbons (e.g., sugars,sugar alcohols, sugar degradation products, etc.) with hydrogen in thepresence of a catalyst. The temperature and pressure conditions for thereaction may be varied depending on the feedstock composition and thedesired products (e.g., oxygenated compounds or hydrocarbons).

FIG. 3 discloses an exemplary method for producing C₄₊ compounds, suchas C₄₊ alcohols, C₄₊ ketones, C₄₊ alkanes, C₄₊ alkenes, C₄₊cycloalkanes, C₄₊ cycloalkenes, an aryl, a fused aryl, an oxygenatedaryl, an oxygenated fused aryl, and mixtures thereof. The disclosedmethod includes catalytically reacting oxygenated hydrocarbons withhydrogen in the presence of a catalyst under conditions sufficient toproduce oxygenated compounds. An oxygenated compound is thencatalytically reacted with another oxygenated hydrocarbon or otherfunctionalized hydrocarbon in the presence of a condensation catalystunder conditions sufficient to produce C₄₊ compounds.

Further description and possible variations of the invention for themethods, catalysts, products, and reactor systems is provided below.

Feedstocks

Feedstocks comprising oxygenated hydrocarbons useful in the process mayoriginate from any source, but are generally derived from biomass. Thefeedstocks may be pure materials, purified mixtures, or raw materialssuch as sugars and starches derived from the processing of corn,sugarcane, beet sugars, pine, rice, wheat, algae, or energy crops. Someapplicable feedstocks are also commercially available and may beobtained as by-products from other processes, such as glycerol frombiodiesel fuel production. The feedstocks can also be intermediatesformed as part of a larger process or in the same process, such as sugaralcohols produced in the initial stage of sugar hydrogenation.

As used herein the terms “lignocellulosic biomass” and “biomass” referto, without limitation, organic materials produced by plants (e.g.,wood, leaves, roots, seeds, stalks, etc.), and microbial and animalmetabolic wastes. Common biomass sources include: (1) agriculturalresidues, such as corn stalks, straw, seed hulls, sugarcane leavings,bagasse, nutshells, and manure from cattle, poultry, and hogs; (2) woodmaterials, such as wood or bark, sawdust, timber slash, and mill scrap;(3) municipal waste, such as waste paper and yard clippings; (4) energycrops, such as poplars, willows, switch grass, pine, miscanthus,sorghum, alfalfa, prairie bluestream, corn, soybean, and the like; (5)residual solids from industrial processes, such as lignin from pulpingprocesses, acid hydrolysis, or enzymatic hydrolysis; and (6)algae-derived biomass, including carbohydrates and lipids frommicroalgae (e.g., Botyococcus braunii, Chlorella, Dunaliell tertiolecta,Gracilaria, Pleurochyrsis carterae, and Sargassum) and macroalgae (e.g.,seaweed). The term also refers to the primary building blocks of theabove, namely, lignin, cellulose, hemicellulose, derivatives thereof,and carbohydrates, such as saccharides of any size (i.e.monosaccharides, disaccharides, trisaccharides, oligosaccharides, orpolysaccharides), sugars, and starches, among others. A person ofordinary skill in the art will appreciate that different terms can beused to refer to the same molecules depending on the context. Forexample, the term “sugar” can include simple sugars, e.g.monosaccharides like glucose or fructose, or complex sugars, e.g.disaccharides like sucrose or maltose or even larger molecules.

The term “oxygenated hydrocarbon” refers to any molecule which can berepresented as C₂₊O₂₊. Examples include without limitation, lignin,cellulose, hemicellulose, derivatives thereof, carbohydrates (e.g.,monosaccharides, disaccharides, oligosaccharides, polysaccharides, andstarches), sugars (e.g., glucose, sucrose, xylose, etc.), sugar alcohols(e.g., diols, triols, and polyols), and sugar degradation products(e.g., hydroxymethylfurfural (HMF), levulinic acid, formic acid, andfurfural).

The term “oxygenated compound” refers to a molecule having two or morecarbon atoms and one or more oxygen atoms, which can herein berepresented as C₂₊O₁₊ The term “monooxygenates” refers to a hydrocarbonmolecule containing two or more carbon atoms and one oxygen atom. Theterm “dioxygenates” refers to a hydrocarbon molecule containing two ormore carbon atoms and two oxygen atoms. The term “polyoxygenates” refersto a hydrocarbon molecule containing two or more carbon atoms and threeor more oxygen atoms.

The feedstock of the present invention comprises: (i) water; (ii)greater than 20 wt % of a plurality of first oxygenated hydrocarbons,the first oxygenated hydrocarbons selected from the group consisting ofmonosaccharides, disaccharides, trisaccharides, oligosaccharides, andcombinations thereof; (iii) between 1 wt % and 40 wt % of a plurality ofsecond oxygenated hydrocarbons, the second oxygenated hydrocarbonscomprising sugar degradation products; and (iv) ash.

The first oxygenated hydrocarbons are selected from the group consistingof monosaccharides, disaccharides, trisaccharides, oligosaccharides, andcombinations thereof. In certain cases, first oxygenated hydrocarbonsare monosaccharides and disaccharides. The first oxygenated hydrocarbonsmay be derived from biomass, particularly cellulose or hemicellulose.Monosaccharides include, without limitation, aldotetrososes,ketotetroses, aldopentoses, ketopentoses, aldohexoses, and ketohexoses.Examples of monosaccharides include without limitation erythrose,threose, erythrulose, arabinose, lyxose, ribose, xylose, ribulose,xylulose, glucose, mannose, galactose, allose, altrose, gulose, idose,talose, psicose, fructose, sorbose, tagatose, or rhamnose. Disaccharidesinclude any combination of two monosaccharides, including, withoutlimitation, sucrose, lactulose, lactose, maltose, trehalose, orcellobiose. Trisaccharides include any combination to threemonosaccharides. Oligosaccharides include any combination of four to 20monosaccharides, and in certain cases, any combination of four to 10monosaccharides. The feedstock comprises a plurality of first oxygenatedhydrocarbons at amounts greater than 20 wt % of the feedstock. In someembodiments, the first oxygenated hydrocarbons may be greater than 25 wt%, greater than 30 wt %, greater than 35 wt %, greater than 40 wt %,greater than 45 wt %, greater than 50 wt %, greater than 55 wt %, orgreater than 60 wt %, of the feedstock.

The second oxygenated hydrocarbons comprise sugar degradation products.The sugar degradation products may be derived from biomass, particularlycellulose or hemicellulose. The sugar degradation product may be anydehydration product of a monosaccharide, disaccharide, trisaccharide,oligosaccharide, or combinations thereof. Common sugar degradationproducts are heterocyclic compounds, organic acids, sugar alcohols,ketones, aldehydes, as well as other products. Heterocyclic compoundsmay include cyclic ether or lactone moieties. Examples of heterocycliccompounds include, without limitation, furan, furfural, orhydroxymethylfurfural, hydroxymethylfuranone, levoglucosan, sorbitan,isomaltol, and humins. Examples of organic acids include, withoutlimitation, levulinic acid, formic acid, pyruvic acid, gluconic acid,glyceric acid, succinic acid, and lactic acid. Examples of sugaralcohols include, without limitation glycol and glycerol. Other productmight include, without limitation, compounds such as glyceraldehyde andglycoaldehyde. The second oxygenated hydrocarbon may be present at anywt % between 1 wt % and 40 wt %, including greater than 2 wt %, greaterthan 3 wt %, greater than 4 wt %, greater than 5 wt %, greater than 6 wt%, greater than 7 wt %, greater than 8 wt %, greater than 9 wt %,greater than 10 wt %, greater than 15 wt %, greater than 20 wt %,greater than 25 wt %, greater than 30 wt %, greater than 35 wt %, andless than 35 wt %, less than 30 wt %, less than 25 wt %, less than 20 wt%, less than 15 wt %, less than 10 wt %, less than 9 wt %, less than 8wt %, less than 7 wt %, less than 6 wt %, less than 5 wt %, less than 4wt %, less than 3 wt %, less than 2 wt %, or any wt % between anyinterval thereof.

The feedstock may include one or more additional oxygenated hydrocarbonshaving two or more carbon atoms and two or more oxygen atoms, i.e.C₂₊O₂₊. The oxygenated hydrocarbons may have an oxygen-to-carbon ratioof between about 0.5:1 to about 1:1.2. In certain cases, the oxygenatedhydrocarbon has 3 to 12 carbon atoms or, and in other cases, 3 to 6carbon atoms, but oxygenated hydrocarbon having more than 12 carbonatoms are capable of being used in the present invention. In someembodiments, the additional oxygenated hydrocarbons comprise greaterthan 1 wt %, greater than 2 wt %, greater than 3 wt %, greater than 4 wt%, greater than 5 wt %, greater than 6 wt %, greater than 7 wt %,greater than 8 wt %, greater than 9 wt %, greater than 10 wt %, greaterthan 15 wt %, greater than 20 wt %, greater than 25 wt %, greater than30 wt %, greater than 35 wt %, greater than 40 wt %, or any wt % betweenany interval thereof of the feedstock.

In one embodiment, the feedstock may include sugar alcohols. The sugaralcohols may be derived from biomass either directly as a sugardegradation product or indirectly. The feedstock containing a firstoxygenated hydrocarbon may be hydrogenated to convert part orsubstantially all of the first oxygenated hydrocarbon into a sugaralcohol (i.e. greater than 50%, greater than 60%, greater than 70%,greater than 80%, greater than 90%, greater than 95%, or any percentagebetween any interval thereof). When part of the first oxygenatedhydrocarbon is hydrogenated to form a sugar alcohol, the feedstock mayfurther comprise a third oxygenated hydrocarbon comprising a sugaralcohol. Method for forming sugar alcohols from the first oxygenatedhydrocarbon are known (see e.g. U.S. patent application Ser. No.12/827,827, the disclosure of which is incorporated herein byreference). In some embodiments, the sugar alcohols comprise greaterthan 1 wt %, greater than 2 wt %, greater than 3 wt %, greater than 4 wt%, greater than 5 wt %, greater than 6 wt %, greater than 7 wt %,greater than 8 wt %, greater than 9 wt %, greater than 10 wt %, greaterthan 15 wt %, greater than 20 wt %, greater than 25 wt %, greater than30 wt %, greater than 35 wt %, greater than 40 wt %, or any wt % betweenany interval thereof.

In one embodiment, the feedstock may include oxygenated hydrocarbonssolvated by a solvent. Non-limiting examples of solvents include:organic solvents, such as ionic liquids, acetone, ethanol,4-methyl-2-pentanone, and other oxygenated hydrocarbons; dilute acids,such as acetic acid, oxalic acid, hydrofluoric acid; bioreformingsolvents; and water. The solvents may be from external sources,recycled, or generated in-situ, such as in-situ generated oxygenatedcompounds (e.g. C₂₊O₂₊ oxygenated hydrocarbons). In some embodiments,the solvent may comprise greater than 1 wt %, greater than 2 wt %,greater than 3 wt %, greater than 4 wt %, greater than 5 wt %, greaterthan 6 wt %, greater than 7 wt %, greater than 8 wt %, greater than 9 wt%, greater than 10 wt %, greater than 15 wt %, greater than 20 wt %,greater than 25 wt %, greater than 30 wt %, greater than 35 wt %,greater than 40 wt %, or any wt % between any interval thereof of thefeedstock.

In one embodiment, the feedstock may include lignin or ligninderivatives. Lignin derivatives include without limitation monomers,dimers, trimers, oligomers, and combinations thereof of phenylpropanoidsthat originate from lignin. Exemplary phenylpropanoids includeparacoumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. Ligninderivatives also include without limitation phenols, methoxyphenols,dimethoxyphenols that originate from lignin. Phenols, methoxyphenols,and dimethoxyphenols may be substituted with an alkyl moiety, alkenylmoiety, hydroxyl moiety, carbonyl moiety, or combinations thereof.Examples include without limitation phenol, 4-methyl-phenol,4-ethyl-phenol, 4-propal2-methoxy-phenol, 4-ethyl-phenol,4-ethyl-2-methoxy-phenol, 4-propyl-phenol, 4-ethyl-2-methoxy-phenol,2,6-dimethoxy-phenol, 2-methoxy-4-propyl-phenol,2-methoxy-3-(2-propenyl)-phenol, 1-(2,5-dimethoxyphenyl)-propanol,2,6-dimethoxy-4-(2-propenyl)-phenol, and combinations thereof. In someembodiments, the lignin or lignin derivatives may comprises greater than0.1 wt %, greater than 0.2 wt %, greater than 0.3 wt %, 0.4 wt %,greater than 0.5 wt %, greater than 0.6 wt %, greater than 0.7 wt %,greater than 0.8 wt %, greater than 0.9 wt %, greater than 1.0 wt %,greater than 1.5 wt %, greater than 2.0 wt %, greater than 2.5 wt %,greater than 3.0 wt %, greater than 3.5 wt %, greater than 4.0 wt %,greater than 4.5 wt %, greater than 5.0 wt %, or any wt % between anyinterval thereof wt % of an aqueous feedstock.

Chemical conversion processes (e.g., bioreforming) can be used toconvert a wide range of compounds typically found in biomass-derivedfeedstocks, including pentoses and hexoses, monomers and oligomers, andhigh concentrations of heterocyclic compounds, to desirable oxygenatedintermediates. In addition to the conventional sugars, chemicalconversion methods can be used to convert some extractives (e.g., fattyacids and phenols) and hydrolysis byproducts (e.g., non-structuralsugars, sugar alcohols, organic acids, etc.) and alcohols. However,catalysts used in chemical conversion processes can be sensitive to theinorganic profile of the heterogeneous carbohydrate feedstock.Therefore, providing a feedstock having a reduced ash componentconcentration, like those shown in Table 2, may provide improvedcatalyst lifetime, product yields, and product distributions.

The ash comprises inorganic materials. Examples include, withoutlimitation, Al, B, Ba, Ca, Cu, Fe, K, Mg, Mn, Na, P, or S, all of whichare found naturally in biomass at various amounts. For the feedstock,the total ash content should be less than 1 wt % of the feedstock. Incertain embodiments, the total ash content is less than 0.5 wt %, lessthan 0.45 wt %, less than 0.4 wt %, less than 0.35 wt %, less than 0.3wt %, less than 0.25 wt %, or less than 0.2 wt %. Two elements having aparticularly large effect on catalyst performance are sulfur andphosphorus. The sulfur concentration may be below 75 ppm and, in certaincases, below 70 ppm, below 65 ppm, below 60 ppm, below 50 ppm, below 45ppm, below 40 ppm, below 35 ppm, below 30 ppm, below 25 ppm, below 20ppm, below 15 ppm, below 10 ppm, below 5 ppm, or below any ppm betweenany interval thereof. The phosphorus concentration may be below 30 ppmand, in certain cases, below 25 ppm, below 20 ppm, below 15 ppm, below10 ppm, below 5 ppm, or below any ppm between any interval thereof.

Production of Feedstocks

Processes for the deconstruction of biomass include, without limitation:(1) thermochemical treatments such as water hydrolysis, acid hydrolysis,alkaline hydrolysis, and/or organosolv pulping; (2) pyrolysis, (3)enzymatic hydrolysis, or (4) catalytic biomass deconstruction. Theprocesses may be used alone or in combination.

In water hydrolysis, the biomass is contacted with water at temperaturesand pressures suitable to hydrolyze cellulose and hemicellulose to theirmonomeric, dimeric, trimeric, or oligomeric components. For cellulose,this includes glucose, while hemicellulose is hydrolyzed to provide, forexample, xylose, galactose, mannose, arabinose, and acetic acid.Hemicellulose is more susceptible to deconstruction by water hydrolysis,so effectively deconstructing the cellulose generally requires hightemperatures. However, the temperatures needed to deconstruct thebiomass will also lead to sugar degradation products of the liberatedsugars. Once complete, the resulting slurry contains residual orunreacted fiber from lignin, and an aqueous solution of the desiredsugars and other hydrolysate products including sugar alcohols and sugardegradation products.

In acid hydrolysis, the biomass is contacted with a mineral acid (e.g.,sulfuric acid, hydrochloric acid, or phosphoric acid) in the presence ofsteam to hydrolyze the cellulose and hemicellulose to their monomeric,dimeric, trimeric, and oligomeric components. For cellulose, thisincludes glucose, while hemicellulose is hydrolyzed to provide, forexample, xylose, galactose, mannose, arabinose, and acetic acid.Sulfuric acid, hydrochloric acid, and phosphoric acid are the three mostcommon mineral acids used for this process. Once complete, the resultingslurry contains the mineral acid, as well as residual or unreacted fiberfrom lignin, and an aqueous solution of the desired sugars and otherhydrolysate products, including sugar alcohols, sugar degradationproducts, phenolics, aromatics, and hydrocarbons. Exemplary hydrolysateproducts include organic acids (e.g., acetic acid, formic acid,propionic acid, malic acid, citric acid, oxalic acid, lactic acid,butyric acid, valeric acid, aconitic acid, caproic acid, 2-furoic acid,vanillic acid, syringic acid, protocatechuic acid, ferulic acid,p-coumaric acid, sinapic acid, gallic acid, glucuronic acid,galacturonic acid, cellobiouronic acid, aldonic acids, aldaric acids,hexanoic acid, heptanoic acid, etc.), phenols (e.g., 4-ethyl phenol,4-ethyl-2-methoxy phenol, 2-methoxy-4-propyl phenol, vanillin, 4-propylsyringol, etc.), cresols, furfural, hydroxymethylfurfural, levulinicacid, formic acid, vitamin E, steroids, long chain hydrocarbons, longchain fatty acids, stilbenoids, flavonoids, terpenoids, aliphatics,lignans, and proteinaceous material.

In alkaline hydrolysis, an aqueous solution of strong base (typicallyOH) is contacted with the biomass to break-down its cellular components.Typically the base is particularly well suited to deconstruct thelignin, but can also deconstruct the hemicellulose and cellulosecomponents. It is difficult, however, to get a high yield of sugarsbecause the alkalis readily degrade the mono- and disaccharides. Thehemicellulose is hydrolyzed by the base to yield xylose, galactose,mannose, arabinose, and acetic acid. Sugar degradation products likeorganic acids and heterocyclic compounds are also readily formed in theprocess. Other hydrolysate products are formed as well, including,without limitation, phenolics, aromatics, and hydrocarbons.

In organosolv pulping, an organic solvent is contacted with the biomassto deconstruct the cellular components. Typically the organic solventsreadily deconstruct the hemicellulose and lignin fractions, butcellulose often may be recalcitrant to the organic solvent. Thehemicellulose is hydrolyzed by the solvents to yield xylose, galactose,mannose, arabinose, and acetic acid. Sugar degradation products, likeorganic acids or heterocyclic compounds, are also readily formed in theprocess. A variety of different solvents are effective to the processincluding, without limitation, alcohols (e.g. methanol and ethanol),diols (e.g. ethylene glycol), triols (e.g. glycerol), ethers (e.g.furfurals), ketones, and phenols. Other hydrolysate products are formedas well, including, without limitation, phenolics, aromatics, andhydrocarbons.

In pyrolysis, the biomass is deconstructed at elevated temperatures inthe absence of oxygen. In certain cases, catalyst may also be present.The resulting bio-oil product is a complex mixture of derivatives of thebiomass components and sugar degradation products like organic acids andheterocyclic compounds, phenolics, aromatics, and hydrocarbons. Inaddition, there is an aqueous phase product that is also produced thatcontains water-soluble products, including water-soluble sugardegradation products such as alcohols, diols, ketones, aldehydes,organic acids, as well as others.

Enzymatic hydrolysis typically involves a thermochemical pretreatmentfollowed by hydrolysis with cellulose enzymes. The thermochemicalpretreatment is used to increase the surface area of the cellulosematerial to allow enzyme penetration. When compared to acid hydrolysisalone, the thermochemical pretreatment steps are generally milder (e.g.,lower mineral acid concentrations, shorter treatment times, etc.). Afteracid pretreatment, base is added to the solution to raise the pH to arange in which the enzyme is active and, in the process, the mineralacid is converted into a mineral salt. Similar to the acid hydrolysisprocess, the hemicellulose is hydrolyzed by the mineral acid to xylose,galactose, mannose, arabinose, and acetic acid. The cellulose ishydrolyzed by the enzymes to glucose. Other hydrolysate products areformed as well, including, without limitation, sugar degradationproducts, phenolics, aromatics, and hydrocarbons.

Catalytic biomass deconstruction involves the use of a heterogeneouscatalyst to hydrolyze the cellulose, hemicellulose and, in someinstances, the lignin to water-soluble oxygenated hydrocarbons. Theoxygenated hydrocarbons include carbohydrates, starches,polysaccharides, disaccharides, monosaccharides, sugars (includingglucose, xylose, galactose, mannose, arabinose), sugar degradationproducts (e.g., hydroxymethylfurfural (HMF), levulinic acid, formicacid, and furfural), sugar alcohols, alditols, polyols, diols, alcohols,ketones, cyclic ethers, esters, carboxylic acids, aldehydes, phenols,cresols and other oxygenated hydrocarbon species.

In addition to the oxygenated hydrocarbons produced by any of thedeconstruction methods, the feedstock further includes lignin, one ormore extractives, one or more ash components, or one or more organicspecies (e.g., lignin derivatives). Extractives include terpenoids,stilbenes, flavonoids, phenolics, aliphatics, lignans, alkanes,proteinaceous materials, and other inorganic products. Ash componentsmay include inorganic materials, such as Al, Ba, Ca, Fe, K, Mg, Mn, P,S, Si, and Zn, whether alone or in combination. The ash components forfive exemplary feedstocks are disclosed in Table 1. Other organicspecies include 4-ethyl phenol, 4-ethyl-2-methoxy phenol,2-methoxy-4-propyl phenol, vanillin, 4-propyl syringol, vitamin E,steroids, long chain hydrocarbons, long chain fatty acids, stilbenoids,etc.

Methods for treating the hydrolysate to reduce ash components,extractives, neutralize hydrolysis media, etc., include physical andchemical separations, such as filtration, ion exchange chromatography,size exchange chromatography, liquid-liquid extraction, solventextraction, distillation, etc. Additional methods for treating thehydrolysate stream will be known to those skilled in the art.

Production of Oxygenated Compounds

The term “bioreforming” refers to, without limitation, processes forcatalytically converting biomass and other carbohydrates to lowermolecular weight hydrocarbons and oxygenated compounds, such asalcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes,dioxygenates, and other polyoxygenated hydrocarbons, using aqueous phasereforming, hydrogenation, hydrogenolysis, hydrodeoxygenation and/orother conversion processes involving the use of heterogeneous catalysts.Bioreforming also includes the further catalytic conversion of suchlower molecular weight oxygenated compounds to C₄₊ compounds. Theoxygenated compounds are prepared by reacting hydrogen with an aqueousfeedstock solution containing water and the oxygenated hydrocarbons overa deoxygenation catalyst containing one or more metals selected fromGroup VIII, Group IVB, Group VB, Group VIB, Group VIIB, Group IB, andGroup IIIB. The APR and deoxygenation catalysts may comprise one or moreof Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt,Au, Ti, Zr, Hf, V, Nb, Ta, La, and Ce, alloys thereof, and mixturesthereof. Exemplary deoxygenation catalysts include Pt, NiSn, PtRe, andPtRuSn, PdAg, PdMoSn, respectively. Various deoxygenation methods,processes, and techniques are described above, all of which areincorporated herein by reference.

The hydrogen may be generated in-situ using aqueous phase reforming(in-situ-generated H₂ or APR H₂), or a combination of APR H₂, externalH₂ or recycled H₂, or just simply external H₂ or recycled H₂. The term“external H₂” refers to hydrogen that does not originate from thefeedstock solution, but is added to the reactor system from an externalsource. The term “recycled H₂” refers to unconsumed hydrogen, which iscollected and then recycled back into the reactor system for furtheruse. External H₂ and recycled H₂ may also be referred to collectively orindividually as “supplemental H₂.” In general, supplemental H₂ may beadded for purposes of supplementing the APR hydrogen, or to increase thereaction pressure within the system, or to increase the molar ratio ofhydrogen to carbon and/or oxygen in order to enhance the productionyield of certain reaction product types, such as diols, ketones, cyclicethers, and alcohols.

The deoxygenation catalysts may be self-supporting (i.e., the catalystdoes not need another material to serve as a support), or the catalystmay be adhered to a support. Such supports include, without limitation,nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria,boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide,chromia, zeolites, tungstated zirconia, titania zirconia, sulfatedzirconia, phosphated zirconia, acidic alumina, silica-alumina, sulfatedalumina, iron aluminate, phosphated alumina, theta alumina, niobia,niobia phosphate, oxides of the foregoing, and mixtures thereof.Nanoporous supports such as zeolites, carbon nanotubes, or carbonfullerene may also be used.

In one embodiment, the catalyst support is zirconia. The zirconia may beproduced via precipitation of zirconium hydroxide from zirconium salts,through sol-gel processing, or any other method. The zirconia may bepresent in a crystalline form achieved through calcination of theprecursor material at temperatures exceeding 400° C., and may includeboth tetragonal and monoclinic crystalline phases. A modifying agent maybe added to improve the textural or catalytic properties of thezirconia. Such modifying agents include, without limitation, sulfate,tungstenate, phosphate, titania, silica, and oxides of Group IIIBmetals, especially Ce, La, or Y.

In another embodiment, the support is tungstated zirconia. Thetungstated zirconia may be produced via impregnation of zirconiumhydroxide with an aqueous solution containing a tungsten salt,precipitation from zirconium and tungsten salts through sol-gelprocessing, or any other method. The tungstated zirconia may be presentin a mixed oxide crystalline form achieved through calcination of theprecursor material at temperatures exceeding 400° C., or temperaturesexceeding 600° C., and may include both tetragonal and monocliniccrystalline zirconia phases as well as polytungsten oxide clusterspresent on the catalyst support surface. A modifying agent may be addedto improve the textural or catalytic properties of the tungstatedzirconia. Such modifying agents include, without limitation,tungstenate, sulfate, phosphate, titania, silica, and oxides of GroupIIIB metals (e.g., Ce, La, or Y).

In another embodiment the catalyst support is tungsten oxide. Tungstenoxide may be prepared via precipitation from a tungsten-containing salt,or other methods.

In another embodiment the catalyst support is niobia phosphate. Niobiaphosphate may be produced via precipitation from niobium- andphosphate-containing salts through sol-gel processing, impregnation ofan aqueous solution of a phosphate solution onto niobium oxide, or othermethods.

In another embodiment the catalyst support is titania. The titania maybe produced via precipitation from titanium salts, through sol-gelprocessing, or any other method. The titania may be present in acrystalline form and may include both anatase and rutile crystallinephases. A modifying agent may be added to improve the textural orcatalytic properties of the titania. Such modifying agents include,without limitation, sulfate, silica, tungstenate, and oxides of GroupIIIB metals (e.g., Ce, La, or Y).

In another embodiment the catalyst support is a transitional alumina,such as theta alumina. The theta alumina may be produced viaprecipitation from aluminum salts, through sol-gel processing, or anyother method. The support may be manufactured through peptization of asuitable aluminum hydroxide, such as bohemite or pseudo-bohemite, withnitric acid in the presence of an organic binder, such as hydroxyethylcellulose. After forming, the support is then calcined at a finaltemperature between about 900° C. to about 1200° C., or greater thanabout 1000° C. A modifying agent may be added to improve the textural orcatalytic properties of the alumina. Such modifying agents include,without limitation, sulfate, silica, Fe, Ce, La, Cu, Co, Mo, or W.

The support may also be treated or modified to enhance its properties.For example, the support may be treated, as by surface-modification, tomodify surface moieties, such as hydrogen and hydroxyl. Surface hydrogenand hydroxyl groups can cause local pH variations that affect catalyticefficiency. The support may also be modified, for example, by treatingit with sulfates, phosphates, tungsten, silanes, lanthanides, alkalicompounds or alkali earth compounds.

Conventional methods for preparing catalyst systems are well known inthe art. Common methods include incipient wetting, evaporativeimpregnation, chemical vapor deposition, wash-coating, magnetronsputtering techniques, and the like. The method chosen to fabricate thedeoxygenation catalyst is not critical to the process, with the provisothat different catalysts and methods of preparation will yield differentresults, depending upon considerations such as overall surface area,porosity, etc.

To produce the oxygenated compounds, the oxygenated hydrocarbon iscombined with water to provide an aqueous feedstock solution having aconcentration effective for causing the formation of the desiredreaction products. The water-to-carbon ratio on a molar basis may befrom about 0.5:1 to about 100:1, including ratios such as 1:1, 2:1, 3:1,4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 25:1, 50:1 75:1, 100:1, andany ratios there-between. The feedstock solution may also becharacterized as a solution having at least about 1.0 weight percent (wt%) of the total solution as an oxygenated hydrocarbon. For instance, thesolution may include one or more oxygenated hydrocarbons, with the totalconcentration of the oxygenated hydrocarbons in the solution being atleast about 1%, 5%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or greater byweight, including any percentages between, and depending on theoxygenated hydrocarbons used. In one embodiment, the feedstock solutionincludes at least about 10%, 20%, 30%, 40%, 50%, or 60% of a sugar, suchas glucose, fructose, sucrose or xylose, or a sugar alcohol, such assorbitol, mannitol, glycerol or xylitol, by weight. Water-to-carbonratios and percentages outside of the above stated ranges are alsoincluded.

In one embodiment the feedstock solution is reacted with hydrogen in thepresence of the deoxygenation catalyst at temperatures, pressures, andweight hourly space velocities effective to produce the desiredoxygenated compounds. The specific oxygenates produced will depend onvarious factors, including the feedstock solution, reaction temperature,reaction pressure, water concentration, hydrogen concentration, thereactivity of the catalyst, and the flow rate of the feedstock solutionas it affects the space velocity (the mass/volume of reactant per unitof catalyst per unit of time), gas hourly space velocity (GHSV), andweight hourly space velocity (WHSV). For example, an increase in flowrate, and thereby a reduction of feedstock exposure to the deoxygenationcatalyst over time, will limit the extent of the reactions that mayoccur, thereby causing increased yield for higher level di- andtri-oxygenates, with a reduction in ketone, alcohol, and cyclic etheryields.

The reaction temperature and pressures may be selected to maintain atleast a portion of the feedstock in the liquid phase at the reactorinlet. It is recognized, however, that temperature and pressureconditions may also be selected to more favorably produce the desiredproducts in the vapor-phase. In general, the reaction should beconducted at process conditions wherein the thermodynamics of theproposed reaction are favorable. For instance, the minimum pressurerequired to maintain a portion of the feedstock in the liquid phase willlikely vary with the reaction temperature. As temperatures increase,higher pressures will generally be required to maintain the feedstock inthe liquid phase, if desired. Pressures above that required to maintainthe feedstock in the liquid phase (i.e., vapor-phase) are also suitableoperating conditions.

In general, the reaction may include a temperature gradient to allowpartial deoxygenation of the oxygenated hydrocarbon feedstock attemperatures below the caramelization point of the feedstock. Includinga temperature gradient helps prevent the oxygenated hydrocarbons in thefeedstock from condensing (e.g., caramelizing) on the catalyst andcreating a substantial pressure drop across the reactor that can lead toits inoperability. The caramelization point, and therefore the requiredtemperature gradient, will vary depending on the feedstock. In oneembodiment, the temperature gradient is from about 80° C. to 300° C., orbetween about 170° C. to 300° C., or between about 200° C. to 290° C. Inanother embodiment, a temperature gradient is not employed.

Operating pressures up to about 2500 psig can be used to help maintainthe carbon backbone and minimize the amount of light organic acids andketones that are formed by increasing the product selectivity towardsalcohols. By increasing operating pressures, the thermodynamics of thereaction favor alcohols to ketones and organic acids, thereby shiftingthe product selectivity, maintaining the carbon backbone, and improvingproduct yields. Light organic acids are particularly undesirableproducts as they are highly corrosive. Producing fewer light organicacids provides more flexibility with regards to materials ofconstruction of a reactor system because corrosion is less of an issue.

In condensed phase liquid reactions, the pressure within the reactormust be sufficient to maintain the reactants in the condensed liquidphase at the reactor inlet. For liquid phase reactions, the reactiontemperature may be greater than 100° C., or 110° C., or 120° C., or 130°C., or 140° C. or 150° C., or 160° C., or 170° C., or 180° C., or 190°C., or 200° C., and less than 300° C., or 290° C., or 280° C., or 270°C., or 260° C., or 250° C., or 240° C., or 230° C., or 220° C. Thereaction pressure may be greater than about 70 psig, or 85 psig, or 100psig, or 115 psig, or 130 psig, or 145 psig, or 160 psig, or 175 psig,or 190 psig, or 205 psig, or 220 psig, or 235 psig, or 250 psig, or 265psig, or 280 psig, or 295 psig, or 310 psig, or 325 psig, or 375 psig,or 425 psig, or 475 psig, or 550 psig, or 625 psig, or 775 psig, or 925psig, or 1050 psig, and less than 2500 psig, or 2450 psig, or 2400 psig,or 2350 psig, or 2300 psig, or 2250 psig, or 2200 psig, or 2150 psig, or2100 psig, or 2050 psig, or 2000 psig, or 1950 psig, or 1900 psig, or1850 psig, or 1800 psig. In certain embodiments, the reactiontemperature is between about 120° C. and 300° C., or between about 200°C. and 300° C., or between about 270° C. and 290° C., and the reactionpressure is between about 145 and 2500 psig, or between about 1000 and2000 psig, or between about 1050 and 1800 psig.

For vapor phase reactions, the reaction may be carried out at atemperature where the vapor pressure of the oxygenated hydrocarbon is atleast about 0.1 atm., but in some cases higher (e.g., 350 psi), and thethermodynamics of the reaction are favorable. This temperature will varydepending upon the specific oxygenated hydrocarbon compound used, but isgenerally greater than about 100° C., or 120° C., or 160° C., or 200°C., or 250° C., and less than about 600° C., or 500° C., or 400° C. forvapor phase reactions. In certain embodiments, the reaction temperatureis between about 120° C. and about 500° C., or between about 250° C. andabout 400° C.

In general, the reaction should be conducted under conditions where theresidence time of the feedstock solution over the catalyst isappropriate to generate the desired products. For example, the WHSV forthe reaction may be at least about 0.01 gram of oxygenated hydrocarbonper gram of catalyst per hour, and, in certain cases, the WHSV is about0.01 to 40.0 g/g hr., including a WHSV of 0.01, 0.025, 0.05, 0.075, 0.1,0.25, 0.5, 0.75, 1.0, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9,2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3,3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7,4.8, 4.9, 5.0, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40g/g hr., and ratios between (including 0.77, 0.78, 0.79, 2.61, 2.62,2.63, etc.).

The hydrogen used in the reaction is may be external hydrogen, but mayinclude in-situ generated hydrogen. The amount (moles) of externalhydrogen or recycled hydrogen introduced to the feedstock may be betweenabout 0-2400%, 5-2400%, 10-2400%, 15-2400%, 20-2400%, 25-2400%,30-2400%, 35-2400%, 40-2400%, 45-2400%, 50-2400%, 55-2400%, 60-2400%,65-2400%, 70-2400%, 75-2400%, 80-2400%, 85-2400%, 90-2400%, 95-2400%,98-2400%, 100-2400%, 200-2400%, 300-2400%, 400-2400%, 500-2400%,600-2400%, 700-2400%, 800-2400%, 900-2400%, 1000-2400%, 1100-2400%, or1150-2400%, or 1200-2400%, or 1300-2400%, or 1400-2400%, or 1500-2400%,or 1600-2400%, or 1700-2400%, or 1800-2400%, or 1900-2400%, or2000-2400%, or 2100-2400%, or 2200-2400%, or 2300-2400% of the totalnumber of moles of the oxygenated hydrocarbon(s) in the feedstock,including all intervals between. When the feedstock solution, or anyportion thereof, is reacted with in-situ generated hydrogen and externalhydrogen or recycled hydrogen, the molar ratio of in-situ generatedhydrogen to external hydrogen (or recycled hydrogen) is at least 1:100,1:50, 1:20; 1:15, 1:10, 1:5; 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1,20:1, 50:1, 100:1 and ratios between (including 4:1, 6:1, 7:1, 8:1, 9:1,11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1 and 19:1, andvice-versa).

Deoxygenation Product Recycle

Recycle streams may be used to maximize product yields and reducecatalyst deactivation. The product of the deoxygenation reactionincludes partially deoxygenated hydrocarbons in addition to the C₂₊O₁₊oxygenated compounds. Partially deoxygenated hydrocarbons include C₂₊O₂₊hydrocarbons (e.g., disaccharides, monosaccharides, sugars, sugaralcohols, alditols, heavy organic acids, and heavy diols, triols, andother polyols). Recycling these partially deoxygenated hydrocarbons backinto the deoxygenation reactor system reduces the carbohydrateconcentration entering the deoxygenation reactor system by diluting thecarbohydrate-rich feedstock solution with partially deoxygenatedhydrocarbons. Diluting the highly reactive carbohydrate feed streamminimizes condensation reactions in the deoxygenation reactor system inwhich the feedstock condenses on the deoxygenation catalyst, fouling thecatalyst, and requiring frequent catalyst changes and/or regeneration.In certain embodiments the recycle to fresh feed weight ratio is in therange of about 0.25-to-1 to 10-to-1, including any ratios between, suchas 0.50, 1.00, 2.50, 4.00, 5.00, and 7.50-to-1.

Reactor System

The reactions described herein may be carried out in any reactor ofsuitable design, including continuous-flow, batch, semi-batch ormulti-system reactors, without limitation as to design, size, geometry,flow rates, etc. The reactor system may also use a fluidized catalyticbed system, a swing bed system, fixed bed system, a moving bed system,or a combination of the above. In one embodiment, the process is carriedout using a continuous-flow system at steady-state equilibrium.

FIG. 1A (without an aqueous recycle stream) and 1B (with an aqueousrecycle stream) are schematic illustrations showing embodiments forconverting a biomass-derived oxygenated hydrocarbon feedstock solutionto a final desired product using a single reactor containing adeoxygenation catalyst on a support. In certain embodiments thefeedstock solution includes a solvent (e.g., water, recycled partiallydeoxygenated hydrocarbons, etc.) combined with oxygenated hydrocarbons,such as carbohydrates (e.g., monosaccharides, disaccharides,oligosaccharides, polysaccharides, and starches), sugars (e.g., glucose,sucrose, xylose, etc.), and sugar degradation products (e.g.,hydroxymethylfurfural (HMF), levulinic acid, formic acid, and furfural).As described above, in certain embodiments the feedstock may alsoinclude ash components, sugar alcohols (e.g., diols, triols, andpolyols), extractives, phenolics, etc. In one embodiment the feedstockis fed via a pump to the deoxygenation reactor system having thedeoxygenation catalyst on a support, where it subsequently reacts withhydrogen to generate oxygenated compounds (e.g., monooxygenates,dioxygenates, ketones, carboxylic acids, cyclic ethers, aldehydes, andalcohols).

In certain embodiments the effluent stream from the reactor contains amixture of water, hydrogen, carbon dioxide, light hydrocarbons (e.g.,alkanes have four or fewer carbon atoms, such as methane, ethane,propane, and butane), monooxygenates, dioxygenates, alcohols, ketones,carboxylic acids, aldehydes, cyclic ethers, and unreacted feedstock. Inone embodiment the mixture is passed through a three-phase separator toseparate the non-condensed gases (such as hydrogen, carbon dioxide,methane, ethane, and propane) from the deoxygenation organic productsstream and the deoxygenation aqueous stream. The non-condensed gases areremoved via a deoxygenation off-gas stream. The non-condensable streamcan be either combusted to create process heat (i.e., heat for drivingthe reaction in the deoxygenation reactor), or sent to a separationsystem where hydrogen can be recovered for recycle back to the hydrogenstream. The deoxygenation aqueous stream, containing partiallydeoxygenated hydrocarbons, may be recycled back to the reactor inlet. Adeoxygenation aqueous stream, including some monooxygenates (e.g.,alcohols), can be used to prevent a build-up of water in the reactorsystem.

Condensation

The oxygenated compounds can be collected and used in industrialapplications, or converted into C₄₊ compounds by condensation reactionscatalyzed by a condensation catalyst. Without being limited to anyspecific theories, it is believed that the condensation reactionsgenerally consist of a series of steps involving: (a) the dehydration ofoxygenates to alkenes; (b) oligomerization of the alkenes; (c) crackingreactions; (d) cyclization of larger alkenes to form aromatics; (e)alkane isomerization; (f) hydrogen-transfer reactions to form alkanes.The reactions may also consist of a series of steps involving: (1) aldolcondensation to form a β-hydroxyketone or β-hydroxyaldehyde; (2)dehydration of the β-hydroxyketone or β-hydroxyaldehyde to form aconjugated enone; (3) hydrogenation of the conjugated enone to form aketone or aldehyde, which may participate in further condensationreactions or conversion to an alcohol or hydrocarbon; and (4)hydrogenation of carbonyls to alcohols, or vice-versa. Othercondensation reactions may occur in parallel, including aldolcondensation, prins reactions, ketonization of acids, and Diels-Aldercondensation.

The condensation catalyst will generally be a catalyst capable offorming longer chain compounds by linking two oxygen containing species,or other functionalized compounds (e.g., olefins), through a newcarbon-carbon bond, and converting the resulting compound to ahydrocarbon, alcohol or ketone. The condensation catalyst may include,without limitation, carbides, nitrides, zirconia, alumina, silica,aluminosilicates, phosphates, zeolites, titanium oxides, zinc oxides,vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides,magnesium oxides, cerium oxides, barium oxides, calcium oxides,hydroxides, heteropolyacids, inorganic acids, acid modified resins, basemodified resins, and combinations thereof. The condensation catalyst mayinclude the above alone or in combination with a modifier, such as Ce,La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, and combinationsthereof. The condensation catalyst may also include a metal, such as Cu,Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo,W, Sn, Os, alloys and combinations thereof, to provide a metalfunctionality.

In certain embodiments the condensation catalyst may include, withoutlimitation, carbides, nitrides, zirconia, alumina, silica,aluminosilicates, phosphates, zeolites (e.g., ZSM-5, ZSM-11, ZSM-12,ZSM-22, ZSM-23, ZSM-35 and ZSM-48), titanium oxides, zinc oxides,vanadium oxides, lanthanum oxides, yttrium oxides, scandium oxides,magnesium oxides, cerium oxides, barium oxides, calcium oxides,hydroxides, heteropolyacids, inorganic acids, acid modified resins, basemodified resins, and combinations thereof. The condensation catalyst mayalso include a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd,Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, to provide a metal functionality.

The condensation catalyst may be self-supporting (i.e., the catalystdoes not need another material to serve as a support), or may require aseparate support suitable for suspending the catalyst in the reactantstream. In certain embodiments the support is selected from the groupconsisting of alumina, silica, and zirconia. In other embodiments,particularly when the condensation catalyst is a powder, the catalystsystem may include a binder to assist in forming the catalyst into adesirable catalyst shape. Applicable forming processes includeextrusion, pelletization, oil dropping, or other known processes. Zincoxide, alumina, and a peptizing agent may also be mixed together andextruded to produce a formed material. After drying, this material iscalcined at a temperature appropriate for formation of the catalyticallyactive phase, which usually requires temperatures in excess of 350° C.Other catalyst supports may include those described in further detailbelow.

In one embodiment the condensation reaction may be performed using acatalyst having acidic functionality. The acid catalysts may include,without limitation, aluminosilicates (zeolites), silica-aluminaphosphates (SAPO), aluminum phosphates (ALPO), amorphous silica alumina,zirconia, sulfated zirconia, tungstated zirconia, tungsten carbide,molybdenum carbide, titania, acidic alumina, phosphated alumina,phosphated silica, sulfated carbons, phosphated carbons, acidic resins,heteropolyacids, inorganic acids, and combinations thereof. In oneembodiment, the catalyst may also include a modifier, such as Ce, La, Y,Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, P, B, Bi, and combinations thereof.The catalyst may also be modified by the addition of a metal, such asCu, Ag, Au, Pt, Ni, Fe, Co, Ru, Rh, Zn, Ga, In, Pd, Ir, Re, Mn, Cr, Mo,W, Sn, Os, alloys and combinations thereof, to provide metalfunctionality, and/or sulfides and oxides of Ti, Zr, V, Nb, Ta, Mo, Cr,W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, P, andcombinations thereof. Tungstated zirconia, an exemplary catalyst for usein the present process, may be modified with Cu, Pd, Ag, Pt, Ru, Ni, Snand combinations thereof. The acid catalyst may be homogenous,self-supporting or adhered to any one of the supports further describedbelow, including supports containing carbon, silica, alumina, zirconia,titania, vanadia, ceria, heteropolyacids, alloys and mixtures thereof.

The condensation catalyst may be a zeolite catalyst. The term “zeolite”as used herein refers not only to microporous crystallinealuminosilicate, but also microporous crystalline metal-containingaluminosilicate structures, such as galloaluminosilicates andgallosilicates. In such instances, In, Zn, Fe, Mo, Ag, Au, Ni, P, Y, Ta,and lanthanides may be exchanged onto zeolites to provide the desiredactivity. Metal functionality may be provided by metals such as Cu, Ag,Au, Pt, Ni, Fe, Co, Ru, Zn, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os,alloys and combinations thereof.

The condensation catalyst may include one or more zeolite structurescomprising cage-like structures of silica-alumina. Zeolites arecrystalline microporous materials with well-defined pore structures.Zeolites contain active sites, usually acid sites, which can begenerated in the zeolite framework. The strength and concentration ofthe active sites can be tailored for particular applications. Examplesof suitable zeolites for condensing secondary alcohols and alkanes maycomprise aluminosilicates, optionally modified with cations, such as Ga,In, Zn, Mo, and mixtures of such cations, as described, for example, inU.S. Pat. No. 3,702,886, which is incorporated herein by reference. Asrecognized in the art, the structure of the particular zeolite orzeolites may be altered to provide different amounts of varioushydrocarbon species in the product mixture. Depending on the structureof the zeolite catalyst, the product mixture may contain various amountsof aromatic and cyclic hydrocarbons.

Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12,ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5, and the conventionalpreparation thereof, is described in U.S. Pat. No. 3,702,886; Re. 29,948(highly siliceous ZSM-5); U.S. Pat. Nos. 4,100,262 and 4,139,600, allincorporated herein by reference. Zeolite ZSM-11, and the conventionalpreparation thereof, is described in U.S. Pat. No. 3,709,979, which isalso incorporated herein by reference. Zeolite ZSM-12, and theconventional preparation thereof, is described in U.S. Pat. No.3,832,449, incorporated herein by reference. Zeolite ZSM-23, and theconventional preparation thereof, is described in U.S. Pat. No.4,076,842, incorporated herein by reference. Zeolite ZSM-35, and theconventional preparation thereof, is described in U.S. Pat. No.4,016,245, incorporated herein by reference. Another preparation ofZSM-35 is described in U.S. Pat. No. 4,107,195, the disclosure of whichis incorporated herein by reference. ZSM-48, and the conventionalpreparation thereof, is taught by U.S. Pat. No. 4,375,573, incorporatedherein by reference. Other examples of zeolite catalysts are describedin U.S. Pat. No. 5,019,663 and U.S. Pat. No. 7,022,888, alsoincorporated herein by reference. An exemplary condensation catalyst isa ZSM-5 zeolite modified with Cu, Pd, Ag, Pt, Ru, Ni, Sn, orcombinations thereof.

As described in U.S. Pat. No. 7,022,888, the condensation catalyst maybe a bifunctional pentasil zeolite catalyst including at least onemetallic element from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn,Cd, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, or a modifier from the group of In, Zn, Fe, Mo, Au, Ag, Y, Sc,Ni, P, Ta, lanthanides, and combinations thereof. The zeolite may havestrong acidic sites, and may be used with reactant streams containing anoxygenated hydrocarbon at a temperature of below 580° C. Thebifunctional pentasil zeolite may have ZSM-5, ZSM-8 or ZSM-11 typecrystal structure consisting of a large number of 5-memberedoxygen-rings (i.e., pentasil rings). In one embodiment the zeolite willhave a ZSM-5 type structure.

Alternatively, solid acid catalysts such as alumina modified withphosphates, chloride, silica, and other acidic oxides may be used in theprocess. Also, sulfated zirconia, phosphated zirconia, titania zirconia,or tungstated zirconia may provide the necessary acidity. Re and Pt/Recatalysts are also useful for promoting condensation of oxygenates toC₅₊ hydrocarbons and/or C₅₊ mono-oxygenates. The Re is sufficientlyacidic to promote acid-catalyzed condensation. In certain embodiments,acidity may also be added to activated carbon by the addition of eithersulfates or phosphates.

The specific C₄₊ compounds produced will depend on various factors,including, without limitation, the type of oxygenated compounds in thereactant stream, condensation temperature, condensation pressure, thereactivity of the catalyst, and the flow rate of the reactant stream asit affects the space velocity, GHSV, LHSV, and WHSV. In certainembodiments, the reactant stream is contacted with the condensationcatalyst at a WHSV that is appropriate to produce the desiredhydrocarbon products. In one embodiment the WHSV is at least about 0.1grams of volatile (C₂₊O₁₋₂) oxygenates in the reactant stream per gramcatalyst per hour. In another embodiment the WHSV is between about 0.1to 10.0 g/g hr., including a WHSV of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 g/ghr., and increments between.

In certain embodiments the condensation reaction is carried out at atemperature and pressure at which the thermodynamics of the proposedreaction are favorable. For volatile C₂₊O₁₋₂ oxygenates the reaction maybe carried out at a temperature where the vapor pressure of the volatileoxygenates is at least about 0.1 atm. (and, in certain cases, a gooddeal higher). The condensation temperature will vary depending upon thespecific composition of the oxygenated compounds. The condensationtemperature will generally be greater than 80° C., or 100° C., or 125°C., or 150° C., or 175° C., or 200° C., or 225° C., or 250° C., and lessthan 600° C., or 500° C., or 450° C., or 425° C., or 375° C., or 325°C., or 275° C. For example, the condensation temperature may be betweenabout 80° C. to 500° C., or between about 125° C. to 450° C., or betweenabout 250° C. to 425° C. The condensation pressure will generally begreater than 0 psig, or 10 psig, or 100 psig, or 200 psig, and less than1500 psig, or 1400 psig, or 1300 psig, or 1200 psig, or 1100 psig, or1000 psig, or 900 psig, or 700 psig. For example, the condensationpressure may be greater than about 0.1 atm., or between about 0 and 1500psig, or between about 0 and 1200 psig.

Condensation Products

The deoxygenation and condensation reactions can be used in theproduction of C₄₊ alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊cycloalkenes, aryls, fused aryls, polycyclic molecules, C₄₊ alcohols,C₄₊ ketones, C₄₊ furans and mixtures thereof. The C₄₊ alkanes and C₄₊alkenes have from 4 to 30 carbon atoms (C₄₋₃₀ alkanes and C₄₋₃₀ alkenes)and may be branched or straight chained alkanes or alkenes. The C₄₊alkanes and C₄₊ alkenes may also include fractions of C₄₋₉, C₇₋₁₄,C₁₂₋₂₄ alkanes and alkenes, respectively, with the C₄₋₉ fractiondirected to gasoline, the C₇₋₁₆ fraction directed to jet fuels, and theC₁₁₋₂₄ fraction directed to diesel fuel and other industrialapplications. Examples of various C₄₊ alkanes and C₄₊ alkenes include,without limitation, butane, butene, pentane, pentene, 2-methylbutane,hexane, hexene, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,2,3-dimethylbutane, heptane, heptene, octane, octene,2,2,4,-trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane,2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene,dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene,pentadecane, pentadecene, hexadecane, hexadecene, heptyldecane,heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene,eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene,trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomersthereof.

The C₄₊ cycloalkanes and C₅₊ cycloalkenes have from 5 to 30 carbon atomsand may be unsubstituted, mono-substituted or multi-substituted. In thecase of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₄₊ alkyl, a straight chain C₁₊alkyl, a branched C₄₊ alkylene, a straight chain C₂₊ alkylene, a phenylor a combination thereof. By way of example, at least one of thesubstituted groups include a branched C₃₋₁₂ alkyl, a straight chainC₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₁₋₁₂ alkylene,a straight chain C₂₋₁₂ alkylene, a phenyl or a combination thereof. Byway of further example, at least one of the substituted groups include abranched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄alkylene, straight chain C₁₋₄ alkylene, straight chain C₂₋₄ alkylene, aphenyl or a combination thereof. Examples of desirable C₅₊ cycloalkanesand C₅₊ cycloalkenes include, without limitation, cyclopentane,cyclopentene, cyclohexane, cyclohexene, methyl-cyclopentane,methyl-cyclopentene, ethyl-cyclopentane, ethyl-cyclopentene,ethyl-cyclohexane, ethyl-cyclohexene, propyl-cyclohexane,butyl-cyclopentane, butyl-cyclohexane, pentyl-cyclopentane,pentyl-cyclohexane, hexyl-cyclopentane, hexyl-cyclohexane, and isomersthereof.

Aryls will generally consist of an aromatic hydrocarbon in either anunsubstituted (phenyl), mono-substituted or multi-substituted form. Inthe case of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenylor a combination thereof. By way of example, at least one of thesubstituted groups include a branched C₃₋₁₂ alkyl, a straight chainC₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene,a phenyl or a combination thereof. By way of further example, at leastone of the substituted groups include a branched C₃₋₄ alkyl, a straightchain C₁₋₄ alkyl, a branched C₃₋₄ alkylene, straight chain C₂₋₄alkylene, a phenyl or a combination thereof. Examples of various arylsinclude, without limitation, benzene, toluene, xylene (dimethylbenzene),ethyl benzene, para xylene, meta xylene, ortho xylene, C₉₊ aromatics,butyl benzene, pentyl benzene, hexyl benzene, heptyl benzene, oxtylbenzene, nonyl benzene, decyl benzene, undecyl benzene, and isomersthereof.

Fused aryls will generally consist of bicyclic and polycyclic aromatichydrocarbons, in either an unsubstituted, mono-substituted, ormulti-substituted form. In the case of mono-substituted andmulti-substituted compounds, the substituted group may include abranched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene,a straight chain C₂₊ alkylene, a phenyl or a combination thereof. By wayof example, at least one of the substituted groups include a branchedC₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄ alkylene,straight chain C₂₋₄ alkylene, a phenyl or a combination thereof.Examples of various fused aryls include, without limitation,naphthalene, anthracene, and isomers thereof.

Polycyclic compounds will generally consist of bicyclic and polycyclichydrocarbons, in either an unsubstituted, mono-substituted, ormulti-substituted form. Although polycyclic compounds include fusedaryls, as used herein the polycyclic compounds generally have at leastone saturated or partially saturated ring unless clear from context thatthe term includes fused aryls. In the case of mono-substituted andmulti-substituted compounds, the substituted group may include abranched C₃₊ alkyl, a straight chain C₄₊ alkyl, a branched C₄₊ alkylene,a straight chain C₂₊ alkylene, a phenyl or a combination thereof. By wayof example, at least one of the substituted groups include a branchedC₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄ alkylene,straight chain C₂₋₄ alkylene, a phenyl or a combination thereof.Examples of various fused aryls include, without limitation,tetrahydronaphthalene and decahydronaphthalene, and isomers thereof.

The C₄₊ alcohols may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ alcohols may be acompound according to the formula R¹—OH, wherein R¹ is a member selectedfrom the group consisting of a branched C₄₊ alkyl, straight chain C₄₊alkyl, a branched C₄₊ alkylene, a straight chain C₄₊ alkylene, asubstituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, asubstituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl,a phenyl and combinations thereof. Examples of desirable C₄₊ alcoholsinclude, without limitation, butanol, pentanol, hexanol, heptanol,octanol, nonanol, decanol, undecanol, dodecanol, tridecanol,tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol,nonyldecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol,tetraeicosanol, and isomers thereof.

The C₄₊ ketones may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ ketone may be acompound according to the formula

wherein R³ and R⁴ are independently a member selected from the groupconsisting of a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, abranched C₃₊ alkylene, a straight chain C₂₊ alkylene, a substituted C₅₊cycloalkane, an unsubstituted C₅₊ cycloalkane, a substituted C₅₊cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl, a phenyl and acombination thereof. Examples of desirable C₄₊ ketones include, withoutlimitation, butanone, pentanone, hexanone, heptanone, octanone,nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone,pentadecanone, hexadecanone, heptyldecanone, octyldecanone,nonyldecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone,tetraeicosanone, and isomers thereof.

In certain embodiments, the lighter fractions of the above, primarilyC₄-C₁₂, may be separated for gasoline use. Moderate fractions, such asC₇-C₁₆, may be separated for jet fuel, while heavier fractions, i.e.,C₁₁-C₂₄, may be separated for diesel use. The heaviest fractions may beused as lubricants or cracked to produce additional gasoline and/ordiesel fractions. The C₄₊ compounds may also find use as industrialchemicals, whether as an intermediate or an end product. For example,the aryls toluene, xylene, ethyl benzene, para xylene, meta xylene,ortho xylene may find use a chemical intermediates for the product ofplastics and other products. Meanwhile, the C₉₊ aromatics and fusedaryls, such as naphthalene, anthracene, tetrahydronaphthalene, anddecahydronaphthalene, may find use as solvents in industrial processes.

Liquid Fuels and Chemicals

The C₄₊ compounds derived from the deoxygenation and condensationreactions as described above can be fractionated and used in liquidfuels, such as gasoline, jet fuel (kerosene) or diesel fuel. The C₄₊compounds can also be fractionated and used in chemical processes, suchas those common to the petro-chemical industry. For example, the productstream from the process can be fractionated to collect xylenes for usein the production of phthalic acid, polyethylene terephthalate (PET),and ultimately renewable plastics or solvents. Benzene can also becollected and processed for the production of renewable polystyrenes,polycarbonates, polyurethane, epoxy resins, phenolic resins, and nylon.Toluene can be collected and processed for the production of toluenediisocyanate, and ultimately renewable solvents, polyurethane foam orTNT, among others.

In one embodiment, the C₄₊ compounds derived from the process areseparated into various distillation fractions by any means known forliquid fuel compositions. In such applications, the product streamhaving at least one C₄₊ compound derived from the process is separatedinto more than one distillation fraction, wherein at least one of thedistillation fractions is a lighter, moderate or heavier fraction. Thelighter fractions, primarily C₄-C₉ i.e., C₄, C₅, C₆, C₇, C₈, and C₉, maybe separated for gasoline use. The moderate fractions, primarily C₇-C₁₄,i.e., C₇, C₈, C₉, C₁₀, C₁₁, C₁₂, C₁₃, and C₁₄, may be separated for useas kerosene, e.g., for jet fuel use. Heavier fractions, primarilyC₁₂-C₂₄, i.e., C₁₂, C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, C₂₂,C₂₃, and C₂₄, may be separated for diesel fuel use. The heaviestfractions, C₂₅₊ and C₃₀₊, i.e., C₂₅, C₂₆, C₂₇, C₂₈, C₂₉, C₃₀, C₃₁, C₃₂,C₃₃, C₃₄, C₃₅, etc., may be used as lubricants, fuel oils, or may becracked to produce additional fractions for use in gasoline, keroseneand/or diesel fractions.

Because the C₄₊ compounds are derived from biomass, the age of thecompounds, or fractions containing the compounds, is less than 500 yearsold, less than 100 years old, less than 40 years old, and less than 20years old, as calculated from the carbon 14 concentration of thecomponent.

The following examples are to be illustrative and should not beconstrued to limit the scope of protection sought, which is defined bythe appended claims.

EXAMPLES Example A

Table 1 provides ash component analyses for five feedstock sugarcompositions.

TABLE 1 Ash component analyses for five feedstocks Commercialfermentation Commercial 42 Exemplary grade glucose DE refined corn #11raw Commercial #5 hydrolysate corn syrup syrup cane sugar sugar RESULT(PPM of total solids) Al 32 <0.5 <0.5 <0.5 4 B <0.5 <0.5 <0.5 24 <0.5 Bant <0.5 <0.5 50 <0.5 Ca 3474 48 2565 3 Cu <0.5 <0.5 <0.5 7 4 Fe 3 <0.5<0.5 21 0 K 921 93 <0.5 7296 26 Mg 733 57 <0.5 994 4 Mn 2 <0.5 0 10 4 Na220 245 2 381 7 P 50 154 17 379 0 S 35 246 2 794 16 Si 52 6 4 144 0 Zn 9<0.5 <0.5 30 <0.5

Example B

Table 2 provides ash component analysis for five samples having reducedash levels. The results in Table 2 indicate the attainment of low sulfurand phosphorus levels. This suggests that these exemplary samples willexhibit a low tendency to foul or poison catalyst employed in theconversion processes.

TABLE 2 Ash component analyses for exemplary feedstocks Sam- Sam- Sam-Sam- Sam- Sam- Sam- ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 ple 8 RESULT(PPM of total solids) Al nt nt nt nt <0.5 <0.5 <0.5 B <0.5 <0.5 <0.5<0.5 <0.5 <0.5 <0.5 Ba <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 nt Ca 2 <0.5 1 <0.59 9 2 Cu <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Fe <0.5 <0.5 <0.5 <0.5 2 3 <0.5 K<0.5 <0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Mg <0.5 <0.5 <0.5 <0.5 3 4 4 Mn <0.5<0.5 <0.5 <0.5 <0.5 <0.5 <0.5 Na 5 5 5 5 58 69 8 P <0.5 <0.5 <0.5 <0.5<0.5 <0.5 <0.5 S <1.5 <1.5 <1.5 <1.5 4 5 <1.5

Example C

Three deoxygenation catalysts (palladium-molybdenum-tin,palladium-ruthenium, and palladium-silver, all on tungstated zirconiasupports) were tested to determine the impact of feedstock concentrationon deoxygenation catalyst performance, specifically in the conversion ofa glucose solution to monooxygenates (e.g., alcohols and ketones).Before the feedstock was introduced, each of the catalysts were reducedusing hydrogen at a space velocity of 700 hr⁻¹, a 2 hour temperaturegradient to 320° C., followed by a 1 hour hydrogen soak. A shell-in-tubereactor system as described in U.S. Pat. No. 7,767,867 to Cortright,which is incorporated herein by reference, was used under the followingconditions: a reactor outlet temperature of 270° C.; a reactor pressureof 1050 psig; and a liquid hour space velocity (LHSV) of 2 mL feed permL catalyst per hour. The hydrogen was provided at a minimum H₂/carbonmolar ratio of 2.

FIG. 2 illustrates the relationship between monooxygenates yield(defined below) and feedstock concentration for each of the threedeoxygenation catalysts. In all cases, glucose conversion was complete,but as concentration decreased, the amount of unidentified aqueous,typically partially deoxygenated sugar species, increases. The increasein partially deoxygenated species is a result of decreased catalystactivity with decreasing sugar concentration.

${{Monooxygenate}\mspace{14mu} {Yield}} = \frac{g\mspace{14mu} {Monooxygenate}\mspace{14mu} {in}\mspace{14mu} {Product}}{g\mspace{14mu} {Feedstock}\mspace{14mu} {Substrate}\mspace{14mu} \left( {{ie}\mspace{14mu} {Glucose}} \right)}$Unidentified  Aqueous = g  Total  Carbon  in  Aqueous − g  Speciated  Carbon   in  Aqueous

Example D

A deoxygenation catalyst comprising palladium, molybdenum, tin, andtungsten metals supported on a monoclinic zirconia support was used totest the conversion of three aqueous sugar feedstock solutions tomonooxygenates. Before the feedstock was introduced, the catalyst wasreduced using hydrogen at a space velocity of 600 hr⁻¹, a 2 hourtemperature gradient to 300° C., followed by a 1 hour hydrogen soak. Ashell-in-tube reactor system as described in U.S. Pat. No. 7,767,867 toCortright, which is incorporated herein by reference, was used under thefollowing conditions: a reactor outlet temperature of 270-280° C.; areactor pressure of 1050 psig; and a weight hour space velocity (WHSV)between 0.75 and 1.00 grams of sugar per gram of catalyst per hour. Thehydrogen was provided at an H₂/Carbon molar ratio of 2.

Table 3 includes a breakdown of common compound classes produced viadeoxygenation. In all cases, complete conversion of the sugars in thefeedstock was achieved resulting in similar product profiles. Alcoholsand cyclic ethers comprise the majority of monooxygenates produced withoverall monooxygenates yields varying between 50 and 60%.

TABLE 3 Deoxygenation product breakdown with various sugar feedstocks.Concentrations are represented as a weight percentage of the totalcarbon entering the system. 45 wt % Glucose 50 wt % 60 wt % 43DE Feed 15wt % Xylose Glucose Corn Syrup Temperature (° C.) 280 270 270 WHSV(1/hr.) 0.75 1.00 0.75 CO + CO₂ 1.8% 2.2% 1.6% Alkane 10.8% 10.3% 11.3%Alcohol 22.3% 27.0% 20.6% Ketone 1.8% 0.8% 2.2% Cyclic Ether 23.9% 29.9%27.2% Acid 1.6% 2.2% 1.8% Diol 6.3% 1.2% 3.2% Polyoxygenate 1.4% 0.7%2.7% Monooxygenate 49.6% 59.4% 52.0% Yield

Table 4 provides the carbon chain length for the products from the threesugar feedstocks. The carbon distribution for the corn syrup and glucosefeeds are very similar with the majority of the products maintaining theC₆ carbon backbone. Similarly, products containing five carbons are moreprevalent in the products with the xylose-containing feedstock. Themixed feedstock, when compared to the glucose and corn syrup feedstocks,shows a higher prevalence of retro aldol condensation (C₂ and C₃)products that are produced from the five carbon sugar.

TABLE 4 Carbon chain length distribution for various sugar feedstocks.Concentrations are represented as a weight percentage of the totalcarbon entering the system. 45 wt % Glucose 50 wt % 60 wt % 43DE Feed 15wt % Xylose Glucose Corn Syrup Temperature (° C.) 280 270 270 WHSV(1/hr.) 0.75 1.00 0.75 CO + CO₂ 1.8% 2.2% 1.6% C₁ 0.3% 0.1% 0.1% C₂ 4.5%3.1% 2.7% C₃ 14.5% 9.6% 9.1% C₄ 5.3% 4.1% 4.1% C₅ 12.8% 7.8% 9.7% C₆31.5% 46.2% 45.9% C₇₊ 4.0% 6.7% 1.8% Unidentified 19.7% 14.0% 21.2%Aqueous

Example E

A 50 wt % sugar feedstock comprising an exemplary composition wasprocessed using a recycle deoxygenation reactor followed by an acidcondensation (AC) reactor as illustrated in FIG. 3.

A platinum and rhenium catalyst on a monoclinic zirconia support wasused in the deoxygenation reactor, while a nickel-modified ZSM-5catalyst was used in the AC reactor.

The deoxygenation reactor was operated with an outlet temperature of260° C. and a pressure of 1050 psig. The AC reactor was operated at atemperature between about 370° C. and 375° C. with an operating pressureof 75 psig. The feedstock was provided at a WHSV of 0.33 grams of feedper grams of deoxygenation catalyst per hour and the recycle to freshfeed ratio for the deoxygenation reactor was 1:1 on a weight basis. Ahydrogen co-feed was used at a ratio of 8 mol H₂ to 1 mol glucoseequivalent fed.

The exemplary sugar compositions were derived from pine biomass usingconcentrated hydrochloric acid hydrolysis. The composition of a 70 wt %exemplary sugar that was diluted to 50 wt % before being fed into thereactor is shown in Table 5 with the contaminant concentrations in Table6.

TABLE 5 Exemplary sugar feedstock composition Feed Component % Glucose29.2 Mannose 20.4 Xylose 10.4 Arabinose 2.6

TABLE 6 Phosphorus and sulfur concentrations of the exemplarycomposition Contaminant P S Concentration (ppm) BDL 3.2

FIG. 4 shows species and carbon number distribution for gasoline rangeproduct with carbon numbers typically of four to ten. The product washighly aromatic and is similar to a reformate product from aconventional petroleum refinery.

Example F

A feedstock solution comprising 50 wt % of an exemplary sugarcomposition was processed using a recycle deoxygenation reactor followedby a dehydration-oligomerization (DHOG) reactor. The deoxygenationcatalyst consisted of palladium, molybdenum, and tin metals on atungstated zirconia support. The DHOG catalyst consisted of palladiumand gold metals on a tungstated zirconia support. A nickel oxide onalumina catalyst was used to hydrotreat the product from the DHOGreactor; the hydrotreated product was distilled to isolate only the jetfuel range material.

The deoxygenation reactor was operated at an outlet temperature of 250°C. and a pressure of 1050 psig. The DHOG reactor was operated at anoutlet temperature of 290° C. and a pressure of 600 psig. The feedstockwas provided at a WHSV of 0.74 grams of feed per grams of deoxygenationcatalyst per hour and the recycle to fresh feed ratio for the recycledeoxygenation reactor was 4:1 on a weight basis. A hydrogen co-feed wasused at a ratio of 10 mol H₂ to 1 mol glucose equivalent fed. Thehydrotreating reactor was operated at a temperature of 290° C., apressure of 800 psig, and a WHSV of 3 grams of feed per grams ofcatalyst per hour.

The exemplary sugar compositions were derived from pine biomass usingconcentrated hydrochloric acid hydrolysis. The composition of a 70 wt %exemplary sugar that was diluted to 50 wt % before being fed into thereactor is shown in Table 7 with the contaminant concentrations in Table8.

TABLE 7 Exemplary sugar feedstock composition Feed Component % Glucose31.3 Mannose 13.3 Xylose 4.38 Arabinose 1.18

TABLE 8 Phosphorus and sulfur concentrations of the exemplarycomposition Contaminant P S Concentration (ppm) BDL BDL

FIG. 5 compares the final hydrotreated and distilled jet fuel productfrom the exemplary sugar feedstock to a conventional jet fuel sample.The sample produced with the exemplary sugar feedstock is primarilyparaffins and naphthenes, and does not include many aromatics orundesirable components that can lead to deposits and build up in jetengines.

The sample produced with the sugar feedstock was also analyzed by theAir Force Research Lab (AFRL) at Wright Patterson Air Force Base and hassatisfactorily completed testing through CAAFI Fuel Readiness Level 3.The product has excellent cold flow properties, high thermal stability,and high energy density. The physical properties meet anticipatedsynthetic fuel specifications (ASTM D 7566). Detailed testing resultsare shown in Table 9.

TABLE 9 Detailed testing results of Jet fuel Specification TestMIL-DTL-83133G Spec Virent Jet Typical JP-8 Requirement (JP-8) RPN(reference) Aromatics, vol % ≦25 1.5   18.8 Olefins, vol % 0.6    0.8Heat of Combustion ≧42.8 43.3   43.3 (measured), MJ/Kg Distillation:IBP, ° C. 142 159 10% recovered, ° C. ≦205 164 182 20% recovered, ° C.174 189 50% recovered, ° C. 203 208 90% recovered, ° C. 260 244 EP, ° C.≦300 290 265 Residue, % vol ≦1.5 2    1.3 Loss, % vol ≦1.5 0    0.8T90-T10, ° C. ≧22 86  62 Flash point, ° C. ≧38 40  51 Freeze Point, ° C.≦−47 <−60 −50 API Gravity @ 60° F. 37.0-51.0 45.4   44.4 Density @ 15°C., kg/L 0.775-0.840 0.800     0.804 Thermal Stability @ 325° C. or 260°C.** Tube Deposit Rating <3 1     1** Change in Pressure, mm Hg ≦25 0  2**JP-8 thermal stability test is done at 260° C., where as alternativefuels, including the Virdia/Virent fuel, are required to pass thethermal stability test at 325° C.

Example G

An aqueous feedstock containing 50 wt % solids from 43 DE corn syrup andup to 5 wt % organic components was converted to oxygenate intermediatesover a deoxygenation catalyst comprising platinum and rhenium loaded ona monoclinic zirconia support. The organic components in the feedstockconsisted of 5 wt % acetic acid or 5 wt % furfural. The aqueous streamwas fed at WHSV of 3 grams of sugar per gram of catalyst per hour over apacked bed of catalyst. The reactor outlet temperature was set to 265°C.

The corn syrup sugars in each of the three feedstocks were completelyconverted by the process. As shown in FIG. 6, the yield of desirablemonooxygenates intermediates (e.g., alcohols and ketones) was improvedwith acetic acid or furfural present in the feedstock. Low net yields ofacids and cyclic ethers indicated that the organic components in thefeedstock were partially converted to products by the deoxygenationcatalyst.

Example H

An aqueous feedstock containing 40 wt % glucose, 10 wt % xylose, and upto 10 wt % organic components was converted to oxygenate intermediatesover a deoxygenation catalyst comprising palladium, molybdenum, and tinloaded on a tungstated-zirconia support. The organic components in thefeedstock consisted of 5 wt % furfural or a combination of 5 wt %furfural and 5 wt % acetic acid. The aqueous feedstock was fed at a WHSVof 0.75 grams of sugar per gram of catalyst per hour over a packed bedof catalyst. The reactor outlet temperature was set to 245° C.

The corn syrup sugars in each of the four feedstocks were completelyconverted by the process. As shown in FIG. 7, the yield of desirablemonooxygenates intermediates (e.g., ketones and alcohols) was improvedwith furfural present in the feedstock. Up to 5 wt % acetic acid couldbe added to the feedstock in addition to 5 wt % furfural withoutsignificant decrease in alcohol and ketone yields compared to afeedstock free of furfural and acetic acid.

Example I

An aqueous feedstock of 50 wt % DE corn syrup was doped with potassiumsulfate to produce a feed with 30-90 ppm sulfur. The feedstock wasconverted to oxygenate intermediates using a platinum and rheniumcatalyst on a monoclinic zirconia support. The reactor conditionsincluded a WHSV of 3 grams of sugar per gram of catalyst per hour and areactor outlet temperature of 255° C. The corn syrup sugars werecompletely converted by the process. Product profiles for the threefeedstocks are illustrated in FIG. 8.

The feedstock with 30 ppm sulfur produced a similar product to theundoped feedstock, with high yields of oxygenate intermediates (e.g.,alcohols and cyclic ethers). The feedstock with 90 ppm sulfur had a highyield of sorbitol (polyoxygenates in FIG. G1), indicating that thepresence of sulfur in the feedstock decreased the catalyst activitysufficiently to prevent further conversion of sugar hydrogenationproducts to desirable monooxygenates.

Example J

Glycerol was used as a model feedstock to facilitate identification ofpartially deoxygenated oxygenate intermediates. An aqueous feedstock of50 wt % glycerol was doped with dipotassium phosphate to produce afeedstock with 27 ppm phosphate. The feedstock was converted tooxygenate intermediates using a palladium, molybdenum, tin catalyst on atungstated-zirconia support. The reactor conditions included a WHSV of 5grams of glycerol per gram of catalyst per hour and a reactor outlettemperature of 255° C.

As shown in FIG. 9 the doped feedstock decreased the catalyst activity,resulting in decreased glycerol conversion and production of desirablemonooxygenated intermediates (e.g., n-propanol).

1. A method for producing oxygenated compounds from a biomass-derivedfeedstock, the method comprising: (a) providing an aqueous feedstock,the aqueous feedstock comprising: (i) water; (ii) greater than 20 wt %of a plurality of first oxygenated hydrocarbons, the first oxygenatedhydrocarbons comprising sugar alcohols; (iii) between 1 wt % and 40 wt %of a plurality of second oxygenated hydrocarbons, the second oxygenatedhydrocarbon comprising sugar degradation products; and (iv) ash, whereinthe ash comprises less than 75 ppm sulfur and less than 30 ppmphosphorous; and (b) reacting at a temperature of less than 300° C. in acondensed liquid phase reaction or at a temperature of less than 600° C.in a vapor phase reaction a portion of the aqueous feedstock withhydrogen in the presence of a catalyst selected from the groupconsisting of (i) a first deoxygenation catalyst comprising palladium,molybdenum, and tin on a zirconia support, and (ii) a second catalystcomprising platinum and rhenium on a zirconia support, to produce areaction product comprising one or more oxygenated compounds selectedfrom the group consisting of an alcohol, a ketone, a cyclic ether, acarboxylic acid, an aldehyde, a diol, and a polyol.
 2. The method ofclaim 1, wherein the aqueous feedstock is prepared by a biomassdeconstruction method and the deconstruction method is selected from thegroup consisting of water hydrolysis, acid hydrolysis, alkalinehydrolysis, organosolv pulping, pyrolysis, enzymatic hydrolysis,catalytic biomass deconstruction, and combinations thereof.
 3. Themethod of claim 2, wherein the aqueous feedstock is further prepared bya treatment method and the treatment method is selected from the groupconsisting of physical separation, chemical separation, neutralization,catalytic reaction, and combinations thereof.
 4. The method of claim 1,wherein the aqueous feedstock comprises greater than 30 wt % of thefirst oxygenated hydrocarbons.
 5. The method of claim 1, wherein theaqueous feedstock comprises greater than 5 wt % of the second oxygenatedhydrocarbons.
 6. The method of claim 1, wherein the aqueous feedstockcomprises less than 20 wt % of the second oxygenated hydrocarbons. 7.The method of claim 1, wherein the second oxygenated hydrocarbonscomprise less than 15 wt % furfurals.
 8. The method of claim 7, whereinthe second oxygenated hydrocarbons comprise greater than 5 wt %furfurals.
 9. The method of claim 7, wherein the second oxygenatedhydrocarbons comprise less than 10 wt % furfurals.
 10. The method ofclaim 1, wherein the ash comprises less than 50 ppm sulfur.
 11. Themethod of claim 1, wherein the ash comprises less than 20 ppmphosphorus.
 12. The method of claim 1, wherein the aqueous feedstockfurther comprises extractives, lignin, lignin derivatives, solids, orcombinations thereof.
 13. (canceled)
 14. The method of claim 1, furthercomprising reacting a portion of the reaction product with acondensation catalyst at a condensation temperature and a condensationpressure to produce C₄₊ compounds selected from the group consisting ofa C₄₊ alcohol, a C₄₊ ketone, a C₄₊ alkane, a C₄₊ alkene, a C₅₊cycloalkane, a C₅₊ cycloalkene, an aryl, and a fused aryl.
 15. Themethod of claim 14, wherein the C₄₊ compounds are distilled to provide acomposition selected from the group consisting of an aromatic fraction,a gasoline fraction, a kerosene fraction, and a diesel fraction.
 16. Themethod of claim 14, wherein the C₄₊ compounds comprise one or more arylsselected from the group consisting of benzene, toluene, xylene,para-xylene, meta-xylene, and ortho-xylene.
 17. A method for producingoxygenated compounds from a biomass-derived feedstock, the methodcomprising: (a) deconstructing biomass with a deconstruction method toproduce an intermediate feedstock, the intermediate feedstock comprisingoxygenated hydrocarbons, ash, extractives, lignin, lignin derivatives,and solids; (b) treating the intermediate feedstock with a treatmentmethod to produce an aqueous feedstock, the aqueous feedstockcomprising: (i) water; (ii) greater than 20 wt % of a plurality of firstoxygenated hydrocarbons, the first oxygenated hydrocarbons comprisingsugar alcohols; (iii) between 1 wt % and 40 wt % of a plurality ofsecond oxygenated hydrocarbons, the second oxygenated hydrocarbonscomprising sugar degradation products; and (iv) ash, wherein the ashcomprises less than 75 ppm sulfur and less than 30 ppm phosphorous; and(c) reacting at a temperature of less than 300° C. in a condensed liquidphase reaction or at a temperature of less than 600° C. in a vapor phasereaction a portion of the aqueous feedstock with hydrogen in thepresence of a catalyst selected from the group consisting of (i) a firstdeoxygenation catalyst comprising palladium, molybdenum, and tin on azirconia support, and (ii) a second catalyst comprising platinum andrhenium on a zirconia support, to produce one or more oxygenatedcompounds selected from the group consisting of an alcohol, a ketone, acyclic ether, a carboxylic acid, an aldehyde, a diol, and a polyol. 18.The method of claim 17, wherein the deconstruction method is selectedfrom the group consisting of water hydrolysis, acid hydrolysis, alkalinehydrolysis, organosolv pulping, pyrolysis, enzymatic hydrolysis,catalytic biomass deconstruction, and combinations thereof.
 19. Themethod of claim 17, wherein the treatment method is selected from thegroup consisting of physical separation, chemical separation,neutralization, catalytic reaction, and combinations thereof.
 20. Themethod of claim 17, the method further comprising (d) reacting a portionof the oxygenated compounds with a condensation catalyst at acondensation temperature and a condensation pressure to produce C₄₊compounds selected from the group consisting of a C₄₊ alcohol, a C₄₊ketone, a C₄₊ alkane, a C₄₊ alkene, a C₅₊ cycloalkane, a C₅₊cycloalkene, an aryl, and a fused aryl.
 21. The method of claim 1,wherein the aqueous feedstock comprises less than 30 wt % of the secondoxygenated hydrocarbons.
 22. The method of claim 1, wherein the aqueousfeedstock comprises less than 35 wt % of the second oxygenatedhydrocarbons.
 23. The method of claim 1, wherein the aqueous feedstockcomprises greater than 40 wt % of the first oxygenated hydrocarbons. 24.The method of claim 1, wherein the aqueous feedstock comprises greaterthan 50 wt % of the first oxygenated hydrocarbons.